负载杂多酸聚砜光催化膜的制备及其可见光催化性能
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摘要
针对可见光催化剂磷钼酸(POM)回收困难的问题,将离子液体单体1-(4-乙烯基苯基)-3-甲基咪唑氯化物(VBMC)在聚砜(PSF)铸膜液内原位聚合,通过相转化法得到具有互穿网络结构的PSF-PVBMC交联膜,并通过电荷交换作用实现磷钼酸在膜表面的固载,得到PSF-PVBMC-POM光催化膜.通过1H-NMR、ATR-FTIR、XPS、SEM等方法对膜结构与性能进行表征,采用该膜对酸性橙Ⅱ进行可见光降解,考察其降解性能及可重复利用性.结果表明:磷钼酸均匀固载在PSF-PVBMC-POM光催化膜上,VBMC含量为6.56 g时,磷钼酸负载量达到最大值0.9 g/cm2;酸性条件更有利于该光催化膜对染料进行降解,pH=1时膜对0.1 g/L酸性橙Ⅱ溶液的降解效率在120 min内达到93%;重复降解20个循环后,膜对酸性橙的降解率仍保持在90%左右.
In view of the difficulties in the recovery of phosphomolybdic acid(POM), the ionic liquid monomer 1-(4-vinyl phenyl)-3-methyl imidazole chloride(VBMC) was polymerized in polysulfone(PSF) casting solution by in-situ polymerization, and the PSF-PVBMC cross-linked membrane with interpenetrating network structure was prepared by phase inversion method, and the phosphomolybdic acid was immobilized on the surface of the membrane by the charge exchange interaction to obtain the PSF-PVBMC-POM photocatalytic membrane. The structure and properties of the membranes were characterized by ~1H-NMR, ATR-FTIR, XPS and SEM. The degradation performance and reusability of PSF-PVBMC-POM photocatalytic membrane were investigated by the degradation experiment of acid orange Ⅱ in visible light. The results showed that phosphomolybdic acid was uniformly immobilized on PSF-PVBMC-POM photocatalytic membrane, and the maximum loading rate of phosphomolybdic acid was 0.9 g/cm~2 when the content of VBMC was 6.56 g. The acidic condition was more conducive to the degradation of dyes by PSF-PVBMC-POM photocatalytic membrane, especially in the condition of pH = 1, the degradation rate of acid orangeⅡ solution of 0.1 g/L reached 93% in 120 min, and can be maintained at 90% after repeated 20 cycles.
In view of the difficulties in the recovery of phosphomolybdic acid(POM), the ionic liquid monomer 1-(4-vinyl phenyl)-3-methyl imidazole chloride(VBMC) was polymerized in polysulfone(PSF) casting solution by in-situ polymerization, and the PSF-PVBMC cross-linked membrane with interpenetrating network structure was prepared by phase inversion method, and the phosphomolybdic acid was immobilized on the surface of the membrane by the charge exchange interaction to obtain the PSF-PVBMC-POM photocatalytic membrane. The structure and properties of the membranes were characterized by ~1H-NMR, ATR-FTIR, XPS and SEM. The degradation performance and reusability of PSF-PVBMC-POM photocatalytic membrane were investigated by the degradation experiment of acid orange Ⅱ in visible light. The results showed that phosphomolybdic acid was uniformly immobilized on PSF-PVBMC-POM photocatalytic membrane, and the maximum loading rate of phosphomolybdic acid was 0.9 g/cm~2 when the content of VBMC was 6.56 g. The acidic condition was more conducive to the degradation of dyes by PSF-PVBMC-POM photocatalytic membrane, especially in the condition of pH = 1, the degradation rate of acid orangeⅡ solution of 0.1 g/L reached 93% in 120 min, and can be maintained at 90% after repeated 20 cycles.
引文
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[2]文晨,余曦,杨志清.强化铁活性炭内循环体系处理含盐染料废水[J].天津工业大学学报,2015,34(1):28-31.WEN C,YU X,YANG Z Q.Treating calciferous dye wastewater by enhanced Fe/granular active carbon(GAC)circulation system[J].Journal of Tianjin Polytechnic University,2015,34(1):28-31(in Chinese)
[3]REISCH M S.New woes may trigger another shakeout for U.S.dye producers[J].Chemical&Engineering News,1993,71(27):9-11.
[4]张华,李祥鹏,张雯,等.功能化锌金属有机骨架对刚果红染料的吸附[J].天津工业大学学报,2018,37(1):26-31.ZHANG H,LI X P,ZHANG W,et al.Adsorption of Congo red dye by organic skeleton of functional zinc metal[J].Journal of Tianjin Polytechnic University,2018,37(1):26-31(in Chinese).
[5]郭玉梅.偶氮染料的生物毒性及其与生物大分子的结合作用[D].济南:山东大学,2011.GUO Y M.Biological toxicity of azo dyes and their binding to biological macromolecules[D].Jinan:Shandong University,2011(in Chinese).
[6]朱虹,孙杰,李剑超.印染废水处理技术[M].北京:中国纺织出版社,2004.ZHU H,SUN J,LI J C.Printing and dyeing wastewater treatment technology[M].Beijing:China Textile Press,2004(in Chinese).
[7]BALDEZ E E,ROBAINA N F,CASSELLA R J.Employment of polyurethane foam for the adsorption of Methylene Blue in aqueous medium[J].Journal of Hazardous Materials,2008,159(2/3):580-586.
[8]HARPREET S R,MANI S B,JAGDEEP S,et al.Removal of dyes from the effluent of textile and dyestuff manufacturing industry:A review of emerging techniques with reference to biological treatment[J].Critical Reviews in Environmental Science&Technology,2005,35(3):219-238.
[9]IZUMI Y,HISANO K,HIDA T.Acid catalysis of silica-included heteropolyacid in polar reaction media[J].Applied Catalysis A General,1999,181(2):277-282.
[10]TANAKA K,PADERMPOLE K,HISANAGA T.Photocatalytic degradation of commercial azo dyes[J].Water Research,2000,34(1):327-333.
[11]LI B,DONG Y,DING Z.Heterogeneous Fenton degradation of azo dyes catalyzed by modified polyacrylonitrile fiber Fe complexes:QSPR(quantitative structure peorperty relationship)study[J].Journal of Environmental Science,2013,25(7):1469-1476.
[12]KORMALI P,DIMOTICALI D,TSIPI D,et al.Photolytic and photocatalytic decomposition of fenitrothion by PW12O403-and Ti O2:A comparative study[J].Applied Catalysis B Environmental,2004,48(3):175-183.
[13]BIBOUM R N,DOUNGMENE F,KEITA B,et al.Poly(ionic liquid)and macrocyclic polyoxometalate ionic self-assemblies:New water-insoluble and visible light photosensitive catalysts[J].Journal of Materials Chemistry,2011,22(2):319-323.
[14]DIAS J A,CALIMAN E,DIAS S C L,et al.Preparation and characterization of supported H3PW12O40,on silica gel:A potential catalyst for green chemistry processes[J].Catalysis Today,2003,85(1):39-48.
[15]HERAVI M M,DERILVAND F,BAMPHARRAM F F.Highly efficient,four-component one-pot synthesis of tetrasubstituted imidazoles using Keggin-type heteropolyacids as green and reusable catalysts[J].Journal of Molecular Catalysis A:Chemical,2007,263(1/2):112-114.
[16]周华锋,李文泽,张丽清.多孔二氧化钛负载型硅钨杂多酸的制备与表征[J].天津师范大学学报:自然科学版,2014,34(2):89-92.ZHOU H F,LI W Z,ZHANG L Q.Synthesis and characterization of silicon tungsten heteropoly acid loaded on porous titania[J].Journal of Tianjin Normal University:Natural Science Edition,2014,34(2):89-92(in Chinese).
[17]GUO Y,HU C,JIANG S,et al.Heterogeneous photodegradation of aqueous hydroxy butanedioic acid by microporous polyoxometalates[J].Applied Catalysis B Environmental,2002,36(1):9-17.
[18]李富民.磷钨酸盐可见光催化降解染料的性能研究[D].上海:东华大学,2011.LI F M.Study on photocatalytic degradation of dyes with phosphotungstic acid[J].Shanghai:Donghua University,2011(in Chinese)
[19]WASSERSCHEID P,KEIM W.Ionic liquids-new“solutions”for transition metal catalysis[J].Angewandte Chemie International Edition,2000,39(21):3772-3789.
[20]张晶晶,王立敏,董淼.负载杂多酸/TiO2可见光下降解甲基橙[J].天津工业大学学报,2008,27(4):45-48.ZHANG J J,WANG L M,DONG M.Photodegradation of Methyl Orange using heteropoly acid incorporated TiO2colloids as photocatalyst under visible-light[J].Journal of Tianjin Polytechnic University,2008,27(4):45-48(in Chinese).
[21]FORGACS E,CSERHATI T,OROS G.Removal of synthetic dyes from wastewaters:A review[J].Environment International,2004,30(7):953-971.
[22]孟建强,马三妮,李景华,等.用于染料降解的聚丙烯催化膜及其制备方法:中国,103316712A[P].2013-09-25.MENG J Q,MA S N,LI J H.et al.Polypropylene catalytic membrane for dyestuff degradation and its preparation methods:CN,103316712A[P].2013-09-25(in Chinese).
[23]MA S,MENG J,LI J,et al.Synthesis of catalytic polypropylene membranes enabling visible-light-driven photocatalytic degradation of dyes in water[J].Journal of Membrane Science,2014,453(3):221-229.